WO2001080992A2 - Rhodium cloth catalyst for partial oxidation of hydrocarbons - Google Patents
Rhodium cloth catalyst for partial oxidation of hydrocarbons Download PDFInfo
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- WO2001080992A2 WO2001080992A2 PCT/US2001/012954 US0112954W WO0180992A2 WO 2001080992 A2 WO2001080992 A2 WO 2001080992A2 US 0112954 W US0112954 W US 0112954W WO 0180992 A2 WO0180992 A2 WO 0180992A2
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- WIPO (PCT)
- Prior art keywords
- catalyst
- rhodium
- gauze
- partial oxidation
- hydrogen
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 186
- 239000010948 rhodium Substances 0.000 title claims abstract description 63
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 56
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 43
- 230000003647 oxidation Effects 0.000 title claims abstract description 39
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 33
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 33
- 239000004744 fabric Substances 0.000 title claims description 19
- 238000000034 method Methods 0.000 claims abstract description 49
- 230000008569 process Effects 0.000 claims abstract description 49
- 239000007789 gas Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 22
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 121
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000000446 fuel Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 28
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 17
- 239000011148 porous material Substances 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000003345 natural gas Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 10
- 239000001294 propane Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 7
- 238000000629 steam reforming Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 3
- 229910000629 Rh alloy Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000011021 bench scale process Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 natural gas) Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000012332 laboratory investigation Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- OFPXSFXSNFPTHF-UHFFFAOYSA-N oxaprozin Chemical compound O1C(CCC(=O)O)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 OFPXSFXSNFPTHF-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B01J35/58—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/386—Catalytic partial combustion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
- C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a process for the catalytic partial oxidation of hydrocarbons (e.g., natural gas), and in particular to a process for oxidizing methane to produce a mixture of carbon monoxide and hydrogen using a bulk rhodium catalyst in the form of metal cloth, such as gauze or felt
- methane is converted into a mixture of carbon monoxide and hydrogen (i.e., synthesis gas or syngas)
- synthesis gas or syngas i.e., synthesis gas or syngas
- the syngas is converted into hydrocarbons.
- Equation 2 In catalytic partial oxidation, natural gas is mixed with air, oxygen-enriched air, or oxygen, and introduced to a catalyst at elevated temperature and pressure.
- the partial oxidation of methane yields a syngas mixture with a H :CO ratio of 2:1, as shown in Equation 2.
- This ratio is more useful for the downstream conversion of the syngas to chemicals such as methanol and to fuels than the H 2 :CO ratio steam reforming.
- the partial oxidation is also exothermic, while the steam reforming reaction is strongly endothermic.
- oxidation reactions are typically much faster than reforming reactions. This allows the use of much smaller reactors for catalytic partial oxidation processes.
- the syngas produced by either steam reforming or partial oxidation may be converted to hydrocarbon products, for example, fuels boiling in the middle distillate range, such as kerosene and diesel fuel, and hydrocarbon waxes by processes such as the Fischer-Tropsch Synthesis.
- hydrocarbon products for example, fuels boiling in the middle distillate range, such as kerosene and diesel fuel, and hydrocarbon waxes by processes such as the Fischer-Tropsch Synthesis.
- the selectivities of catalytic partial oxidation to the desired products, carbon monoxide and hydrogen are controlled by several factors. One of the most important factors is the choice of catalyst structure. For successful operation on a commercial scale, the catalytic partial oxidation process must be able to achieve a high conversion of the methane feedstock at high gas hourly space velocities, while maintaining high selectivity of the process to the desired products of carbon monoxide and hydrogen. Accordingly, there has been an effort to investigate catalysts that provide high selectivity for specified products and have structures that promote partial oxidation of hydro
- Certain specialized catalysts are known to be suitable for other, unrelated catalytic reactions.
- platinum/rhodium alloy gauze catalysts typically about 5-15 wt % rhodium, are used industrially for the catalytic synthesis of hydrogen cyanide, as well as for the catalytic oxidation of ammonia to nitric acid.
- gauze catalysts are typically mechanically durable.
- Platinum/rhodium catalysts used for hydrogen cyanide and nitric acid synthesis typically have lives of several months before being removed for remanufacturing by reclaiming up to 99 % of the metal and using it to make new catalyst.
- a characteristic of platinum/rhodium catalysts however is a tendency to undergo surface rea ⁇ angement.
- Some platinum group gauze catalysts have been studied as hydrogen synthesis catalysts.
- M. Fathi et al. Catal. Today, 42, 205-209 (1998) disclose the catalytic partial oxidation of methane over Pt, Pt/Rh, Pt/Ir and Pd gauze catalysts at contact times of 0.00021 to 0.00033 seconds.
- Single gauze catalysts were tested in a quartz reactor at 700°C to 1100°C and it was observed that, although high selectivities to carbon monoxide were observed at high temperatures, the selectivity to hydrogen gas was low, "below 30% in most cases.”
- K. Heitnes Hofstad, et. al. Catalysis Letters 36, 25-30 disclose: "Partial oxidation of methane has been studied on a Pt gauze catalyst under conditions where the conversion of O 2 was not complete. The results show that at these very low space times high selectivities of CO are obtained, but low selectivities of H 2 (are obtained) even at temperatures above 800 °C.”
- the present invention provides a catalyst and a process for the catalytic partial oxidation of a hydrocarbon feedstock by contacting a feed stream comprising the hydrocarbon feedstock and an oxygen-containing gas with a catalyst in a reaction zone maintained at conversion-promoting conditions that are effective to produce an effluent stream comprising carbon monoxide and hydrogen.
- the catalyst preferably includes high surface area bulk rhodium. More preferably, the catalyst is in the form of at least one layer of rhodium cloth.
- rhodium cloth refers to a mechanically fixed arrangement of metal wire in a substantially planar configuration, and is intended to include rhodium gauze and rhodium felt.
- the present catalysts are preferably pretreated to activate the catalyst by oxidation in air at a temperature of between about 300°C and about 1200°C, preferably between about 900°C and about 1000°C.
- the air oxidation pretreatment is carried out for a period of time of about one half to four hours.
- the preferred catalysts allow effective partial oxidation of the feed gas with high selectivity, together with high methane conversion. CO and H 2 selectivities of at least 90% and methane conversion rates of at least 90% are achieved. Further, the preferred catalysts are durable and have long lived activity.
- the prefe ⁇ ed catalysts can typically be used without replacement for a period of at least about six months.
- the present gauze and felt catalysts are preferably made of wire of about 0.025 to about 0.25 mm diameter, preferably about 0.1 mm diameter.
- the gauze catalyst preferably includes two or more layers of gauze, and more preferably from about 5 to about 100 layers.
- a preferred gauze layer is about 20 to about 100 mesh, preferably about 40 to about 80 mesh.
- Co ⁇ espondingly, felt densities are from about 10% to about 50%, preferably 35%.
- the felt thickness is preferably from about 5 mm to about 50 mm.
- the preferred ranges of operating conditions for using the present catalysts include temperatures of about 800°C to about 1300°C, preferably from about 1000°C to about 1200° C, and pressures of about 110 kPa to about 3000 kPa, preferably from about 500 kPa to about 3000 kPa.
- the feed stream is preferably preheated to from about 50°C to about 700°C, and preferably to about 400°C, before contacting the catalyst.
- Typical space velocities for the process are from about 60,000 hr "1 to about 20,000,000 hr "1 , and are preferably from about 150,000 hr "1 to about 10,000,000 hr "1 .
- Figure 1 is an exploded schematic view of a gauze catalyst according to one embodiment
- Figures 2i-iii are SEM micrographs of a rhodium gauze catalyst
- Figure 3 is a magnified view of a catalyst bundle of comprising layers of gauze according to one embodiment of the present invention
- Figures 4i-vi are SEM micrographs of a rhodium gauze catalyst after use viewed from the top (i-i ⁇ ) and bottom (iv-vi);
- Figures 5i-vi are SEM micrographs of a platinum/rhodium gauze catalyst (previously used HCN catalyst) after use viewed from the top (i-iii) and bottom (iv-vi);
- Figure 6 is a schematic drawing of a quartz reactor suitable for laboratory scale tests of the catalysts of the preferred embodiment;
- Figure 7 is a schematic of the bench scale testing unit for the catalysts of the prefe ⁇ ed embodiment
- Figure 8 is a chart of results of reaction light-off tests of a rhodium gauze catalyst
- Figure 9 is an exploded schematic view of a felt catalyst of the preferred embodiment.
- a prefe ⁇ ed gauze catalyst structure 10 in accordance with the present invention comprises a plurality of woven layers of gauze 15 each made from a plurality of wires 18.
- the passages between the wires are hereinafter termed "pores" 22.
- a path 26 shows the connection between two pores 22, which are part of a network of pores.
- gas or liquid entering pore 30 can reach pore 34 by way of pore 32.
- the gauze of the prefe ⁇ ed embodiment comprises a flexible screen of about 20 to about 100 mesh (0.84 mm to about 0.15 mm) and preferably about 40 to about 80 mesh (0.37 mm to about 0.18 mm).
- the gauze is made of wire that is preferably about 0.025 mm to about 0.25 mm diameter and preferably about 0.1 mm. While one layer of gauze may be used in some instances, it is generally prefe ⁇ ed to use a bundle of two or more layers of gauze, and preferably 5 to about 100 layers, as the catalyst, more preferably about 15-40 layers.
- a prefe ⁇ ed embodiment of the present catalyst includes a stack of more than one layer of gauze disks, for example 25 layers.
- each layer preferably comprises rhodium wire that has been woven to form a gauze.
- the layers may be aligned or may be shifted in alignment with respect to each other, as shown in Figure
- the layers can be randomly oriented with respect to each other. While the shape of the catalyst bundle, or of a single layer of catalyst, will vary according to its application, the stack is preferably cylmd ⁇ cal so that it can be used in a cylmd ⁇ cal quartz reactor
- the prefe ⁇ ed catalyst includes at least a metal catalytically active for synthesis gas production.
- Suitable metals include rhodium, platinum, and rhodium in combination with Pt, Ru, Ir, NI, Au, Pd, Ti, Re, or V
- Metallic catalysts can be supported or unsupported Suitable cloth-type supports include base metal wire, such as Fe, Cr, and Al, and combinations of Fe, Cr, and Al
- the metals commonly used as wire catalyst supports typically have excellent high temperature strength and good ductility, and can be drawn into wire easily and inexpensively.
- Wire catalyst supports may be treated so as to form a surface layer that acts as a bar ⁇ er and prevents diffusion of catalytic metal from the surface into the bulk metal of the support Further details concerning the treatment of the metallic catalyst support to form a diffusion bar ⁇ er are contained in U.S Patent Application 09/626,894 filed July 27, 2000, and entitled “Catalytic Partial Oxidation Processes and Catalytic Diffusion Bar ⁇ er Coating,” hereby incorporated herein by reference.
- rhodium wire containing at least 90 wt % rhodium performs surpnsingly well as a catalyst
- a rhodium catalyst and a catalyst comp ⁇ sing 85 wt % platinum/15 wt % rhodium catalyst, respectively, are shown as viewed by scanning electron microscopy after use as a partial oxidation catalyst.
- Figures 4 ⁇ /5 ⁇ and 4 ⁇ v/5 ⁇ v show the top and bottom, respectively, of their respective catalysts at 50 times magnification
- the present rhodium catalyst exhibits supe ⁇ or catalytic durability and long active life
- the catalysts process of the present invention can be used to prepare a mixture of carbon monoxide and hydrogen from any gaseous hydrocarbon having a low boiling point.
- the hydrocarbon feedstock is in the gaseous phase when contacting the catalyst.
- the catalysts are suitable for the partial oxidation of methane, natural gas, associated gas or other sources of light hydrocarbons having 1 to 5 carbon atoms.
- Natural gas is mostly methane, but it can also contain up to about 15 mole % ethane, propane and butane.
- the present process can be used for the conversion of gas from naturally occurring reserves of methane, which can also contain carbon dioxide, nitrogen and hydrogen sulfide.
- a prefe ⁇ ed feed for the present process comprises at least 50% by volume methane, more preferably at least 75% by volume, and most preferably at least 80% by volume.
- the hydrocarbon feedstock is preferably contacted with the present catalyst in a reaction zone as a mixture with an oxygen-containing gas, preferably pure oxygen.
- the methane-containing feed and the oxygen-containing gas are mixed in such amounts to give a carbon (i.e., carbon in methane) to oxygen ratio from about 1.25:1 to about 3.3:1, more preferably from about 1.3: 1 to about 2.3:1, and most preferably from about 1.5:1 to about 2.2:1.
- the syngas generation can take place at atmospheric or superatmospheric pressures, with the latter being preferred.
- the present process can be operated at pressures of from about 110 kPa to about 3000 kPa, and is preferably carried out at pressures between about 500 kPa and 2800 kPa.
- the catalysts of the prefe ⁇ ed embodiment are preferably used at temperatures between about 800°C and about 1300°C, and preferably from about 1000°C to about 1200°C.
- the hydrocarbon feedstock and the oxygen-containing gas are preferably pre-heated to between about 50°C and about 700°C, and preferably to about 300°C -500°C , before contacting the catalyst.
- the hydrocarbon feedstock and the oxygen-containing gas can be passed over the catalyst at a variety of space velocities.
- Typical space velocities for the present process are from about 60,000 hr "1 to about 20,000,000 hr "1 , preferably from about 150,000 hr "1 to about 10,000,000 hr "1 .
- the catalyst is preferably pretreated by oxidation in air. Preferred oxidation conditions include a temperature between about 300°C and 1200°C, preferably between about 900°C and 1000°C. Further, the exposure of the catalyst to air preferably proceeds for about one half to four hours.
- a reactor 110 suitable for laboratory investigation of the catalyst of the prefe ⁇ ed embodiments is shown in schematic.
- This reactor resembles in shape a reactor suitable for indust ⁇ al catalysis, but is scaled down in size
- a reactor constructed in this manner was used to perform the examples set out below.
- the partial oxidation reactions were done with a 19 mm O.D. x 13 mm I.D. quartz reactor 110 with a circular bundle 120 of gauze disks (12 mm O.D.) held between two 5 mm x 12 mm alpha-alumma foam disks 130, which served as radiation shields.
- the inlet radiation shield also aids in uniform dist ⁇ bution of the feed gases.
- the gauze and the disks were wrapped with an alumina cloth to obtain a single cylinder 140 of 13 mm diameter and about 15 mm height.
- the catalyst was tightly forced inside the reactor to minimize gas by-pass.
- a band heater was fitted around the quartz reactor. The band heater was used to supply thermal energy to light off the reaction and to preheat the feed gases. After light off, no heating was provided to the reaction zone Thus, the reaction proceeded autothermally.
- Two Type S thermocouples 150 one at each end of the gauze stack, were used to monitor the reaction temperature
- syngas unit 200 included a gas supply system.
- Syngas unit 200 is illustrated in Figure 7 for methane as the fuel.
- syngas unit 200 and the gas supply system are adapted to use a simulated natural gas mixture as the fuel.
- the gas supply system includes a methane supply line 210, an oxygen supply line 220, and a nitrogen supply line 230
- Methane supply line 210 has a propane tie-in 240.
- the propane tie-in is preferably used for starting up the syngas reaction because the ignition temperature of a propane/air flame is lower than that of a methane/air flame.
- Nitrogen is added at about 5 % by volume as an inert tracer component Unit 200 is controlled by a computer (not shown), for example by a Texas Instruments Model 545 PLC system interfaced to a PC using a Wonderware Human-Machine Interface Program
- the methane and oxygen gases are mixed together at room temperature and the mixed gas fed to reactor 110 with or without preheating
- the reaction takes place at 4 psig, for example, and on the catalyst surface.
- Product gas mixtures may be analyzed for methane, oxygen, carbon monoxide, hydrogen gas, carbon dioxide, and nitrogen gas, using any known analysis equipment.
- This system was used to test the catalysts of the following examples
- the methane-containing and oxygen gases were mixed at room temperature and the mixed gas was fed to the reactor with or without preheating
- the product gas mixture was analyzed for Cu t , O 2 , CO, H 2 , CO 2 and N 2 using a gas chromatograph equipped with a thermal conductivity detector.
- GHSV gas hourly space velocity
- Pre-H is the preheat temperature
- Cat-T is the top of the catalyst bed temperature
- Cat-B is the bottom of the catalyst bed temperature
- NG is a simulated natural gas mixture consisting of 7 volume % ethane and 3 volume % propane the rest being methane.
- the catalyst consisted of 25 layers of 60 mesh (.25 mm) rhodium gauze.
- the catalyst consisted of 40 layers of 40 mesh (0.4 mm) Pt (85%)/Rh (15%) gauze.
- Catalyst 40 layers of 40 mesh Pt (85%)/Rh (15%) gauze
- the unit was shut down because of equipment problems on day 2 and was re-started with a new set of thermocouples on day 4.
- the run continued from day 4 until day 65 without interruption.
- high and low grade methane was used as feed.
- the low grade methane contained 5-10% ethane, 1-3% propane, and some carbon dioxide.
- the high grade methane contained 99 % methane by volume.
- the flow rate and the pre-heat were modified as shown in Table 5, causing the fuel conversion to increase by more than 10%, while maintaining high CO conversion.
- the catalyst temperature decreased from about 1200°C to about 1100°C gradually over the course of the 82 days of catalyst run time.
- the pressure was increased to 2 atm at constant mass flow rate. The change in pressure did not appear to affect the conversion and selectivity appreciably.
- the first group of days includes days 28-40, examples 34-42.
- the methane/oxygen ratio ranged from 1.60 to 1.75
- the preheat temperature ranged from 615-630 °C
- the flow rate was 8.0
- the second group of days includes days 68-78, examples 71-85.
- the methane/oxygen ratio ranged from 1.66-1.71
- the preheat temperature ranged from 390-470
- the molar ratio of methane to oxygen was 1.66, the preheat temperature was 470°C, and the flow rate was 8 NLPM.
- a rhodium gauze catalyst can have a lifetime of up to 1-2 years, depending on operating conditions.
- One measure of the lifetime is the half-life, that is the duration of time over which the catalytic activity, such as molar % methane conversion, decreased by one-half from its initial value. For the present catalyst the half-life appears to be about 1-2 years.
- Catalyst 25 layers of 60 mesh Rh gauze two 5 mm x 12 mm and 40 ppi alpha-alumina foam disks
- Tests were performed to determine conditions sufficient for light-off.
- Reactor and catalyst are the same as in Examples 1-12 and 14-83, with the exception of the number of layers of catalyst.
- Various catalyst pretreatments were tested.
- the catalyst, pretreatment, and light-off conditions are given in Table 5.
- the catalyst of Example 90 was subsequently oxidized in air at 500 °C for 4 hours and light-off was attempted.
- the catalyst was subsequently reduced in flowing hydrogen at 600 °C for 12 hours and light-off was attempted. It is believed that the reduction in hydrogen was complete and the catalyst did not differ significantly from fresh catalyst.
- the catalyst bundles was divided into at least 4 bundles of 3 layers and one bundle of 5 layers. These served as the catalyst for Examples 85, 87, 88, 89, and 86, respectively.
- Example 85 The catalyst of Example 85 was subsequently reduced in flowing hydrogen for 12 hours. It is believed that the reduction in hydrogen was complete and the catalyst did not differ significantly from fresh catalyst. This catalyst then served as the catalyst for Example 84.
- the catalyst of Example 91 was freshly prepared. Referring now to Figure 8, the results of tests for reaction light-off are shown. The results show that the lowest light-off temperature was obtained for a pretreatment of oxidation in air at about 900°C for about four hours. The results also show that no reaction was achieved using untreated catalyst. For each catalyst for which light-off was achieved using 22 volume % propane in air, no light-off was achieved using 11 volume % propane in air. For the catalyst of Example 86 light-off was subsequently achieved at 360 C with llvolume % propane in air.
- an alternative preferred catalyst structure 50 comprises layers of felt 55 made from random lengths of wire 59, which have been sintered together to form a cloth.
- the spaces or passages between the wires are hereinafter termed "pores" 63.
- a path 72 illustrates the connection between pores.
- gas or liquid entering pore 75 can reach pore 89 by way of pore 63.
- the felt preferably is composed of random lengths of wire sintered together under pressure at elevated temperature.
- the felt is made from about 0.025 mm to about 0.25 mm diameter wire, preferably, about 0.1 mm.
- Felt densities are from about 10% to about 50% by volume, preferably, 35%.
- the felt thickness is preferably from about 5 mm to about 50 mm.
- pure rhodium wire is used to form the felt.
- the felt is preferably shaped to conform to the inside of a reactor.
- rhodium gauze is exemplary of a bulk metal catalyst having a high surface area and a mechanically durable structure.
- the catalyst made from one or more layers of a metal cloth.
- the term metal cloth refers to a mechanically fixed a ⁇ angement of metal wire in a substantially planar configuration.
- the metal cloth of the present invention includes wire in various configurations such as woven, knitted, fused, and the like. Gauze and felt are exemplary of metal cloth structures.
- the catalyst preferably is made from metal in a network structure defining a network including substantially planar pores and passages connecting at least a portion of the pores.
- the network of pores is preferably a ⁇ anged geometrically such that a volume of gas therein is constrained to remain near the catalyst surface.
- the metal network may be regular, as for a single layer of gauze, or may be i ⁇ egular, as with a layer of felt. Alternatively, the metal network may have elements of both regularity and i ⁇ egularity, as with a plurality of layers of gauze that are not aligned with each other. Still further, the catalyst structure preferably includes a large metallic surface area forming a reactive interface. It is believed that, in this manner, the dependence of reaction dynamics on mass transfer is minimized, so that the conversion rate of the catalyst may be optimized. Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent.
Abstract
Description
Claims
Priority Applications (2)
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AU2001255556A AU2001255556A1 (en) | 2000-04-20 | 2001-04-20 | Rhodium cloth catalyst for partial oxidation of hydrocarbons |
CA002406525A CA2406525A1 (en) | 2000-04-20 | 2001-04-20 | Rhodium cloth catalyst for partial oxidation of hydrocarbons |
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US19879100P | 2000-04-20 | 2000-04-20 | |
US60/198,791 | 2000-04-20 | ||
US09/838,124 | 2001-04-19 | ||
US09/838,124 US6746658B2 (en) | 2000-04-20 | 2001-04-19 | Rhodium cloth catalyst for partial oxidation of hydrocarbons |
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WO2001080992A2 true WO2001080992A2 (en) | 2001-11-01 |
WO2001080992A3 WO2001080992A3 (en) | 2002-02-28 |
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PCT/US2001/012954 WO2001080992A2 (en) | 2000-04-20 | 2001-04-20 | Rhodium cloth catalyst for partial oxidation of hydrocarbons |
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US (1) | US6746658B2 (en) |
AU (1) | AU2001255556A1 (en) |
CA (1) | CA2406525A1 (en) |
WO (1) | WO2001080992A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7226574B2 (en) | 2003-05-16 | 2007-06-05 | Velocys, Inc. | Oxidation process using microchannel technology and novel catalyst useful in same |
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AU2003295465A1 (en) * | 2002-11-11 | 2004-06-03 | Conocophillips Company | Stabilized alumina supports, catalysts made therefrom, and their use in partial oxidation |
GB2450506A (en) * | 2007-06-26 | 2008-12-31 | James Macbeth | Reduction of greenhouse gas emmission |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4491640A (en) * | 1980-12-09 | 1985-01-01 | Osaka Gas Company Limited | Catalyst for combustion at low temperatures and process for producing same |
US4863893A (en) * | 1986-08-06 | 1989-09-05 | Engelhard Corporation | Low temperature light off ammonia oxidation |
US5232891A (en) * | 1990-09-12 | 1993-08-03 | W. C. Heraeus Gmbh | Process for the manufacture of a gauze for a catalytic converter and a gauze for a catalytic converter manufactured according thereto |
US5278124A (en) * | 1991-06-17 | 1994-01-11 | Johnson Matthey, Inc. | Low pressure drop, high surface area ammonia oxidation catalyst |
EP0629578A1 (en) * | 1993-06-18 | 1994-12-21 | Shell Internationale Researchmaatschappij B.V. | Process for the catalytic partial oxidation of hydrocarbon |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4087259A (en) * | 1974-09-20 | 1978-05-02 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Process for partially oxidizing hydrocarbons |
EP0303438A3 (en) | 1987-08-14 | 1989-12-27 | DAVY McKEE CORPORATION | Production of synthesis gas from hydrocarbonaceous feedstock |
ES2127241T3 (en) | 1992-06-24 | 1999-04-16 | Shell Int Research | PROCEDURE FOR PARTIAL CATALYTIC OXIDATION OF HYDROCARBONS. |
US5648582A (en) | 1993-08-20 | 1997-07-15 | Regents Of The University Of Minnesota | Stable, ultra-low residence time partial oxidation |
IT1272532B (en) | 1993-08-27 | 1997-06-23 | Snam Progetti | PARTIAL CATALYTIC OXIDATION PROCESS OF NATURAL GAS TO OBTAIN SYNTHESIS GAS AND FORMALDEHYDE |
CO4370053A1 (en) | 1993-11-29 | 1996-10-07 | Shell Int Research | PROCESS FOR PARTIAL CATALYTIC OXIDATION OF HYDROCARBONS |
DZ1918A1 (en) | 1994-08-02 | 2002-02-17 | Shell Internaional Res Mij B V | Process for partial catalytic oxidation of hydrocarbons. |
US5654491A (en) | 1996-02-09 | 1997-08-05 | Regents Of The University Of Minnesota | Process for the partial oxidation of alkanes |
WO1997031738A1 (en) | 1996-02-27 | 1997-09-04 | Astro Met, Inc. | Porous materials and method for producing |
US5883138A (en) | 1997-04-25 | 1999-03-16 | Exxon Research And Engineering Company | Rapid injection catalytic partial oxidation process and apparatus for producing synthesis gas (law 562) |
US6254807B1 (en) | 1998-01-12 | 2001-07-03 | Regents Of The University Of Minnesota | Control of H2 and CO produced in partial oxidation process |
-
2001
- 2001-04-19 US US09/838,124 patent/US6746658B2/en not_active Expired - Fee Related
- 2001-04-20 WO PCT/US2001/012954 patent/WO2001080992A2/en not_active Application Discontinuation
- 2001-04-20 AU AU2001255556A patent/AU2001255556A1/en not_active Abandoned
- 2001-04-20 CA CA002406525A patent/CA2406525A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4491640A (en) * | 1980-12-09 | 1985-01-01 | Osaka Gas Company Limited | Catalyst for combustion at low temperatures and process for producing same |
US4863893A (en) * | 1986-08-06 | 1989-09-05 | Engelhard Corporation | Low temperature light off ammonia oxidation |
US5232891A (en) * | 1990-09-12 | 1993-08-03 | W. C. Heraeus Gmbh | Process for the manufacture of a gauze for a catalytic converter and a gauze for a catalytic converter manufactured according thereto |
US5278124A (en) * | 1991-06-17 | 1994-01-11 | Johnson Matthey, Inc. | Low pressure drop, high surface area ammonia oxidation catalyst |
EP0629578A1 (en) * | 1993-06-18 | 1994-12-21 | Shell Internationale Researchmaatschappij B.V. | Process for the catalytic partial oxidation of hydrocarbon |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7226574B2 (en) | 2003-05-16 | 2007-06-05 | Velocys, Inc. | Oxidation process using microchannel technology and novel catalyst useful in same |
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CA2406525A1 (en) | 2001-11-01 |
US6746658B2 (en) | 2004-06-08 |
AU2001255556A1 (en) | 2001-11-07 |
US20020176817A1 (en) | 2002-11-28 |
WO2001080992A3 (en) | 2002-02-28 |
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